JPH10503422A - Cobalt on alumina catalyst - Google Patents
Cobalt on alumina catalystInfo
- Publication number
- JPH10503422A JPH10503422A JP8506133A JP50613396A JPH10503422A JP H10503422 A JPH10503422 A JP H10503422A JP 8506133 A JP8506133 A JP 8506133A JP 50613396 A JP50613396 A JP 50613396A JP H10503422 A JPH10503422 A JP H10503422A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- catalyst
- surface area
- transition alumina
- alumina support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000010941 cobalt Substances 0.000 title claims abstract description 102
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 101
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000007704 transition Effects 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000005470 impregnation Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- -1 silicate ions Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/392—Metal surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
(57)【要約】 コバルト表面積が、30ｍ2／コバルトｇより大きく、好ましくは50ｍ2／コバルトｇより大きく、最も好ましくは80ｍ2／コバルトｇより大きい、３乃至40重量％のコバルトを含有する、遷移アルミナ支持体上のコバルト触媒。 (57) Abstract: Cobalt surface area greater than 30 m 2 / g of cobalt, preferably greater than 50 m 2 / g of cobalt, most preferably greater than 80 m 2 / g of cobalt, containing from 3 to 40% by weight of cobalt; Cobalt catalyst on transition alumina support.
Description
【発明の詳細な説明】 アルミナ触媒上のコバルト発明の分野 本願発明は、アルミナ触媒上のコバルト及びそれを製造する方法に関する。発明の背景 触媒において、コバルトは通常、シリカ、珪酸アルミニウム、アルミナのよう な担体上に固定される。 これらの触媒において、有用なコバルト原子は、コバルト粒子の表面において 露出されるものである。露出されない（すなわち、表面においてではない）コバ ルト原子は、触媒反応に参与しない。 コバルトは、高価な金属であり、触媒としての使用を最適にするために、触媒 の（露出したコバルト原子の数／コバルト原子の総数）比をできるだけ増加させ 、コバルトｇ当りコバルト表面積を増大させることが必須である。 欧州特許公開13,275号により、コバルトイオン、シリケートイオン及び固体の 多孔性担体粒子の反応混合物が調製されそしてコバルトイオン及びシリケートイ オンの共沈物を固体の多孔性担体粒子上に形成させる、担持された共沈コバルト -シリカ触媒を製造することが知られている。得られたコバルト-シリカ触媒は、 150乃至350ｍ2／ｇのＢＥＴ総表面積及び５乃至20ｍ2／コバルトｇのコバルト表 面積を有する。 又、米国特許第4,591,579号により、遷移金属（例えば、コバルト、ニッケル 又は銅）の不溶性の塩基性化合物をそのような金属塩の水溶液からアルカリ沈殿 剤で沈殿させ、その後に、この化合物を珪酸塩溶液と反応させる、珪酸- 遷移金 属塩触媒の調製の方法を提供することも知られている。実施例５では、コバルト 表面積が8.9ｍ2／触媒ｇである触媒が記載されている。 “Stoichiometries of H2 and C0 Adsorptions on cobalt”、Journal of Cat alysis 85、63-77頁（1984年）では、67頁、表１において、異なる担体上のコバ ルト触媒が記載されている。その総最大Ｈ2取り込みから、触媒のｇ当り コバルト表面積及びコバルトｇ当りのコバルト表面積を算出することは可能であ る。シリカ触媒上のコバルトでは、コバルトのｇ当りのコバルト表面積は６乃至 65ｍ2／ｇの範囲であり、遷移アルミナ触媒上のコバルトでは、コバルトのｇ当 りコバルト表面積は15乃至26ｍ2／ｇであることが分かる。 従って、シリカ上のコバルト触媒では、コバルトのｇ当り高いコバルト表面積 を有するコバルト触媒が存在するが、遷移アルミナ上のコバルト触媒では、存在 しない。 それにもかかわらず、遷移アルミナ上のコバルト触媒は、他のコバルト触媒よ りいくつの明確な利点を有する。 第一には、遷移アルミナ上のコバルト触媒は、シリカ上のコバルト触媒よりも 押出により付形させることが容易であり、得られる触媒の機械的強度はより高い 。 水が存在する反応において（例えば、メタン化、Fisher Tropsch）、シリカは 不安定である。しかし、アルミナはそのような条件下においてより安定である。 従って、今まで得られたものよりも高い、コバルトのｇ当りのコバルト表面積 を有する、遷移アルミナ上のコバルト触媒に対する必要性がある。 本願発明の第一の目的は、今まで得られたものよりも高い、コバルトのｇ当り のコバルト表面積を有する、遷移アルミナ上のコバルト触媒を提供することであ る。 本願発明の第二の目的は、そのような触媒を製造する方法を提供することであ る。試験及び定義 ｉ）コバルト表面積 約0.5ｇの試料を分析に用いた。金属表面積を算出するのに用いる重量は、予 備処理後に得られたものである。この予備処理の間に、試料をガス抜きし、120 ℃で真空下で乾燥させた。予備処理した試料を次に還元する。250ml／分の流量 で水素ガスを試料に通しながら試料を３℃／分の速度で425℃に加熱する。なお 、同じ水素流れで試料を425℃で18時間維持する。真空下で10分間に亘り試料を4 50℃まで加熱する。その試料を真空下で450℃で２時間維持する。 純粋な水素ガスを用いて150℃において化学吸着を行う。自動分析プログラム を用いて、水素の800mmHgまでの完全等温線を測定する。 この方法は、300乃至800mmHgの間の化学吸着等温線の直線部分を０圧力に外挿 して化学吸着されたガスの容量を算出する。 すべての場合において下記の等式を用いて金属表面積を算出する。 式中、 Ｖ＝水素のml／ｇでの取り込み ＳＦ＝化学量論係数（コバルトにおけるＨ2では２であると仮定する。）、 Ａ＝コバルトの１つの原子により占有される面積（0.0662nm2であると仮定され る） を表わす。 この等式は、Micromeretics in Operators Manual for ASAP 2000 Chemi Syst em V 1.00、Appendix C，Part No．200-42808-01，1991年１月18日により開示さ れている。 ii）遷移アルミナ 遷移アルミナは、“Ullmans Encyklopaedie der technischen Chemie”4.，ne ubearbeitete und erweiterte Auflage，Band 7(1974)，298-299頁に定義されて いる。 その文献では、遷移アルミナをいくつかの分類に分けている。 γ- グループ γ- グループに含まれるのは、γ-Al203を除けば、η-Al203及びχ-Al203のよ うなすべて低温形態である。それらは、400乃至750℃での水酸化アルミニウムの 焼成で形成される。 アルミナのγ- グループ形態の比表面積は、150乃至400ｍ2／ｇの範囲である 。 δ- グループ δ−グループのアルミナは、すべての高温形態、例えば、δ- 、θ- 及びχ- Al203が含まれる。δ−グループのアルミナは、γ- グループのアルミナを約800 ℃以上で加熱するときに生成される。 アルミナのδ−グループ形態の比表面積は、50乃至150ｍ2／ｇの範囲である。本願発明の一般的な記載 コバルト表面積が、30ｍ2／コバルトｇより大きく、好ましくは40ｍ2／コバル トｇより大きく、より好ましくは50ｍ2／コバルトｇより大きく、さらにより好 ましくは80ｍ2／コバルトｇより大きい、３乃至40重量％のコバルトを含有する 、遷移アルミナ支持体上のコバルト触媒を提供することが本願発明の第一の目的 である。 好ましくは、遷移アルミナ支持体は、γ- アルミナ又はθ- アルミナであり、 より好ましくはθ- アルミナである。 好ましくは、コバルト触媒は、５乃至20重量％のコバルト、より好ましくは10 乃至20重量％のコバルトを含有する。 コバルトアムミンカーボネートの水溶液中の遷移アルミナのスラリーを60℃乃 至110℃の温度に加熱し、コバルトヒドロキシカーボネートを沈殿させるために 、次に、得られた生成物を乾燥させそして焼成させる、コバルト表面積が、30ｍ2 ／コバルトｇより大きい、３乃至40重量％のコバルトを含有する、遷移アルミ ナ支持体上のコバルト触媒を製造する方法を提供することが本願発明の第二の目 的である。任意には、焼成させた生成物をさらに還元し得る。 好ましくは、遷移アルミナ支持体は、γ- アルミナ又はθ- アルミナであり、 より好ましくはθ- アルミナである。 コバルトアムミンカーボネートの水溶液で遷移アルミナ粒子を飽和させ、過剰 の溶液を濾過により除去し、得られた生成物を60℃乃至110℃の温度に加熱し、 コバルトヒドロキシカーボネートを沈殿させるために、次に、得られた生成物を 乾燥させそして焼成させる、コバルト表面積が、30ｍ2／コバルトｇより大きい 、３乃至40重量％のコバルトを含有する、遷移アルミナ支持体上のコバルト触媒 を製造する方法を提供することが本願発明の第三の目的である。 好ましくは、遷移金属支持体は、γ- アルミナ又はθ- アルミナであり、より 好ましくはθ- アルミナである。 連続する、含浸及び沈殿工程は、コバルト含量を増大させるために用いられ、 200乃至600℃の温度における焼成処理の間に、沈降されたコバルトヒドロキシカ ーボネートは、酸化コバルトに変換される。 次に、その生成物を、200乃至600℃の温度において、好ましくは350乃至550℃ において水素ガスで活性化し、次に任意に不動態化する。発明の特定の記載 本願発明をさらに下記の実施例において記載する。実施例１ ｉ）含浸溶液の調製 35％の水酸化アンモニウム溶液の1764.0ｇを秤量し（比重0.88）（ＢＤＨから 入手可能）、そして脱イオン化水73.5ｇを添加した。炭酸アンモニウム312.5ｇ （Merckから入手可能）を添加し、攪拌し始めた。穏やかに35℃に加熱し、粉末 を溶解するのを補助した。完全に溶解させたときに、塩基性炭酸コバルト（Merc kから入手でき、47乃至55重量％のコバルトを含有する）350ｇをゆっくりと添加 した。約２時間攪拌し続けた。ブフナー漏斗により濾過した。 ii）θ- アルミナ支持体の含浸 θ- アルミナを100ｇ秤量し、ビーカーに入れ、0.5ｌの含浸溶液を添加した。 10分後、含浸した押出物をブフナー漏斗上に置き、過剰の液体を排出させた。次 に、その生成物を室温で１時間、次に、80℃で１時間そして最後に120℃で一晩 （16時間）乾燥させた。最後に、乾燥させた生成物を、回転式焼成器を用いて35 0℃における空気流れ中で２時間焼成させた。実施例２ 実施例１において含浸の後にそして焼成の前に得られた乾燥させた生成物を実 施例１、ii）の下に記載されているように、再び含浸し、実施例１、ii）の下に 記載されているように乾燥させた。 最後に、乾燥させた生成物を、回転式焼成器を用いて350℃における空気流れ 中で２時間焼成させた。実施例３ 実施例２において含浸の後でそして焼成の前に得られた乾燥させた生成物を実 施例１、ii）の下に記載されているように、再び含浸し、実施例１、ii）の下に 記載されているように乾燥させた。 最後に、乾燥させた生成物を、回転式焼成器を用いて350℃における空気流れ 中で２時間焼成させた。実施例４ 実施例３において含浸の後でそして焼成の前に得られた乾燥させた生成物を実 施例１、ii）の下に記載されているように、再び含浸し、実施例１、ii）の下に 記載されているように乾燥させた。 最後に、乾燥させた生成物を、回転式焼成器を用いて350℃における空気流れ 中で２時間焼成させた。 実施例１乃至４で得られた生成物を分析した。その結果は下記の通りである。 非常に低いコバルト含量を有し、しかし従来技術において得られたものに匹敵 するコバルト表面積（触媒ｇ当り）を有することを可能にする、非常に高いコバ ルト表面積（コバルトｇ当り）を有する、アルミナ支持体におけるコバルト触媒 が得られることがわかった。 活性化された後に、実施例３による触媒を、プローブとしてトルエンを用いて 芳香族物質の水素化における触媒活性において試験した。 反応条件： 圧力：40バールＨ2 ＬＨＳＶ：３ 水素流れ：15ml／分 温度：200℃ 触媒投入：６ml（すなわち５ｇ） トルエンの水素化生成物への変換は62％であり、本願発明の生成物が、水素化 触媒として用いられることができることを証明した。DETAILED DESCRIPTION OF THE INVENTION Cobalt on alumina catalystField of the invention The present invention relates to cobalt on an alumina catalyst and a method for producing the same.Background of the Invention In catalysts, cobalt is usually found in silica, aluminum silicate, and alumina. Immobilized on a suitable carrier. In these catalysts, the useful cobalt atoms form at the surface of the cobalt particles. What is exposed. Edge not exposed (ie not on the surface) The ruto atom does not participate in the catalytic reaction. Cobalt is an expensive metal and, to optimize its use as a catalyst, The ratio of (number of exposed cobalt atoms / total number of cobalt atoms) It is essential to increase the cobalt surface area per g of cobalt. According to European Patent Publication No. 13,275, cobalt ions, silicate ions and solid A reaction mixture of porous carrier particles is prepared and cobalt ions and silicate Supported coprecipitated cobalt forming on coprecipitate on solid porous carrier particles -It is known to produce silica catalysts. The resulting cobalt-silica catalyst is 150-350mTwo/ G BET total surface area and 5-20mTwo/ Cobalt g cobalt table With area. Also, according to U.S. Pat. No. 4,591,579, transition metals (e.g., cobalt, nickel Or copper) insoluble basic compounds from aqueous solutions of such metal salts with alkali Silicate-transition gold, after which the compound is reacted with a silicate solution. It is also known to provide a method for the preparation of genus salt catalysts. In Example 5, cobalt Surface area is 8.9mTwo/ Catalyst g is described. “Stoichiometries of HTwo and C0 Adsorptions on cobalt ”, Journal of Cat alysis 85, pages 63-77 (1984), page 67, Table 1 shows that Catalysts are described. The total maximum HTwoFrom incorporation, per g of catalyst It is possible to calculate the cobalt surface area and the cobalt surface area per g of cobalt. You. For cobalt on silica catalyst, the cobalt surface area per g of cobalt is 6 to 65mTwo/ G of cobalt on a transition alumina catalyst. Cobalt surface area is 15-26mTwo/ G. Thus, for a cobalt catalyst on silica, a high cobalt surface area per gram of cobalt There is a cobalt catalyst having do not do. Nevertheless, the cobalt catalyst on transition alumina is not as good as other cobalt catalysts. It has several distinct advantages. First, the cobalt catalyst on transition alumina is better than the cobalt catalyst on silica. Easy to shape by extrusion, resulting in higher mechanical strength of the catalyst . In reactions where water is present (eg, methanation, Fisher Tropsch), silica It is unstable. However, alumina is more stable under such conditions. Thus, a higher surface area of cobalt per gram of cobalt than previously obtained There is a need for a cobalt catalyst on transition alumina having The first object of the present invention is to achieve a higher cobalt gram per gram than previously obtained. To provide a cobalt catalyst on transition alumina having a cobalt surface area of You. A second object of the present invention is to provide a method for producing such a catalyst. You.Testing and definition i) Cobalt surface area About 0.5 g of sample was used for analysis. The weight used to calculate the metal surface area is It is obtained after the preparatory treatment. During this pretreatment, the sample was vented and 120 Dried under vacuum at ° C. The pretreated sample is then reduced. 250ml / min flow rate The sample is heated to 425 ° C. at a rate of 3 ° C./min while passing hydrogen gas through the sample. Note that The sample is maintained at 425 ° C. for 18 hours with the same flow of hydrogen. Apply the sample for 4 minutes under vacuum. Heat to 50 ° C. The sample is maintained under vacuum at 450 ° C. for 2 hours. Chemisorption is performed at 150 ° C. using pure hydrogen gas. Automatic analysis program The complete isotherm of hydrogen up to 800 mmHg is measured using. This method extrapolates the linear part of the chemisorption isotherm between 300 and 800 mmHg to zero pressure. To calculate the volume of the chemisorbed gas. In all cases, the metal surface area is calculated using the equation below. Where: V = uptake of hydrogen in ml / g SF = stoichiometric coefficient (H in cobaltTwoNow assume that it is 2. ), A = area occupied by one atom of cobalt (0.0662 nmTwoIs assumed to be ) Represents This equation is described in the Micromeretics in Operators Manual for ASAP 2000 Chemi Syst em V 1.00, Appendix C, Part No. 200-42808-01, disclosed on January 18, 1991 Have been. ii) Transition alumina Transition alumina is described in “Ullmans Encyklopaedie der technischen Chemie” 4., ne ubearbeitete und erweiterte Auflage, as defined in Band 7 (1974), pages 298-299 I have. The literature classifies transition alumina into several categories. γ-group Included in the γ-group are η-Al203 and χ-Al203, except for γ-Al203. All are in low temperature form. They are made of aluminum hydroxide at 400-750 ° C. It is formed by firing. Specific surface area of alumina γ-group form is 150-400mTwo/ G range . δ-group The alumina of the δ-group has all high temperature forms, such as δ-, θ- and χ- Al203 is included. The alumina of the δ-group is approximately 800 Produced when heated above ℃. The specific surface area of the δ-group form of alumina is 50 to 150 mTwo/ G range.General description of the invention Cobalt surface area is 30mTwo/ Greater than cobalt g, preferably 40mTwo/ Kobal Larger than g, more preferably 50mTwo/ Greater than cobalt g, even better Preferably 80mTwoContaining from 3 to 40% by weight of cobalt, greater than / g of cobalt It is a first object of the present invention to provide a cobalt catalyst on a transition alumina support It is. Preferably, the transition alumina support is γ-alumina or θ-alumina, More preferably, it is θ-alumina. Preferably, the cobalt catalyst comprises 5 to 20% by weight of cobalt, more preferably 10 to 20% by weight. Contains about 20% by weight of cobalt. Slurry transition alumina in aqueous solution of cobalt ammine carbonate at 60 ° C Heating to a temperature of 110 ° C to precipitate cobalt hydroxycarbonate The product obtained is then dried and calcined, the cobalt surface area being 30 mTwo / Transition aluminum containing 3-40% by weight of cobalt, greater than g of cobalt It is a second object of the present invention to provide a method for producing a cobalt catalyst on a It is a target. Optionally, the calcined product may be further reduced. Preferably, the transition alumina support is γ-alumina or θ-alumina, More preferably, it is θ-alumina. Saturate the transition alumina particles with an aqueous solution of cobalt ammine carbonate and add excess Is removed by filtration and the resulting product is heated to a temperature of 60 ° C to 110 ° C, To precipitate cobalt hydroxycarbonate, the resulting product is then Dried and fired, cobalt surface area is 30mTwo/ Greater than cobalt g Cobalt catalyst on transition alumina support containing from 3 to 40% by weight of cobalt It is a third object of the present invention to provide a method for producing. Preferably, the transition metal support is γ-alumina or θ-alumina, and more Preferred is θ-alumina. Successive impregnation and precipitation steps are used to increase the cobalt content, During the calcination treatment at a temperature of 200 to 600 ° C., the precipitated cobalt hydroxyca Carbonate is converted to cobalt oxide. Next, the product is brought to a temperature of 200-600 ° C., preferably 350-550 ° C. And then optionally passivated.Specific description of the invention The present invention is further described in the following examples.Example 1 i) Preparation of impregnation solution Weigh 1764.0 g of 35% ammonium hydroxide solution (specific gravity 0.88) (from BDH Available), and 73.5 g of deionized water was added. 312.5 g of ammonium carbonate (Available from Merck) was added and stirring was started. Gently heat to 35 ° C and powder To help dissolve the When completely dissolved, basic cobalt carbonate (Merc 350 g), which is available from K and contains 47-55% by weight of cobalt) did. Stirring was continued for about 2 hours. Filtered through a Buchner funnel. ii) Impregnation of θ-alumina support 100 g of θ-alumina was weighed, placed in a beaker, and 0.5 l of the impregnating solution was added. After 10 minutes, the impregnated extrudate was placed on a Buchner funnel to drain excess liquid. Next The product at room temperature for 1 hour, then at 80 ° C. for 1 hour and finally at 120 ° C. overnight Dry (16 hours). Finally, the dried product is transferred to a rotary calciner for 35 Calcination was carried out in a stream of air at 0 ° C. for 2 hours.Example 2 The dried product obtained in Example 1 after impregnation and before calcining was obtained. Re-impregnation as described under Example 1, ii) and under Example 1, ii) Dry as described. Finally, the dried product is subjected to air flow at 350 ° C using a rotary calciner. Baked for 2 hours.Example 3 The dried product obtained in Example 2 after impregnation and before calcining was obtained. Re-impregnation as described under Example 1, ii) and under Example 1, ii) Dry as described. Finally, the dried product is subjected to air flow at 350 ° C using a rotary calciner. Baked for 2 hours.Example 4 The dried product obtained in Example 3 after impregnation and before calcining was obtained. Re-impregnation as described under Example 1, ii) and under Example 1, ii) Dry as described. Finally, the dried product is subjected to air flow at 350 ° C using a rotary calciner. Baked for 2 hours. The products obtained in Examples 1 to 4 were analyzed. The results are as follows. Has very low cobalt content, but comparable to that obtained in the prior art Very high edge area, which makes it possible to have a high cobalt surface area (per g catalyst) Cobalt catalyst on alumina support having a specific surface area (per g of cobalt) Was obtained. After being activated, the catalyst according to example 3 was used with toluene as probe The catalytic activity in the hydrogenation of aromatics was tested. Reaction conditions: Pressure: 40 bar HTwo LHSV: 3 Hydrogen flow: 15ml / min Temperature: 200 ° C Catalyst charge: 6 ml (ie 5 g) The conversion of toluene to hydrogenated products is 62%, indicating that the product of the present invention is hydrogenated. It has been proved that it can be used as a catalyst.
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Claims (1)
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| GB9415554A GB9415554D0 (en) | 1994-08-02 | 1994-08-02 | Cobalt on alumina catalysts |
| GB9415554.6 | 1994-08-02 | ||
| PCT/EP1995/002836 WO1996004072A1 (en) | 1994-08-02 | 1995-07-17 | Cobalt on alumina catalysts |
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| JP (1) | JP3514463B2 (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007038217A (en) * | 2005-07-30 | 2007-02-15 | Oxeno Olefinchemie Gmbh | Hydrogenation catalyst, and catalytic hydrogenation method for ester-containing aldehyde mixture |
Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0003961D0 (en) * | 2000-02-21 | 2000-04-12 | Ici Plc | Catalysts |
| AU2005204343B2 (en) * | 2000-05-19 | 2006-12-07 | Johnson Matthey Plc | Methods of making catalysts with high cobalt surface area |
| EA005420B1 (en) * | 2000-05-19 | 2005-02-24 | Джонсон Мэтти Плс | Catalysts with high cobalt surface area |
| US6914423B2 (en) * | 2000-09-05 | 2005-07-05 | Cascade Microtech, Inc. | Probe station |
| US7621887B2 (en) * | 2000-10-10 | 2009-11-24 | Meridian Medical Technologies, Inc. | Wet/dry automatic injector assembly |
| GB0030170D0 (en) * | 2000-12-11 | 2001-01-24 | Norske Stats Oljeselskap | Fischer-tropsch catalyst |
| US7452844B2 (en) † | 2001-05-08 | 2008-11-18 | Süd-Chemie Inc | High surface area, small crystallite size catalyst for Fischer-Tropsch synthesis |
| RU2210432C1 (en) * | 2001-12-21 | 2003-08-20 | Институт катализа им. Г.К. Борескова СО РАН | Catalyst and method of preparing hydrocarbons and their oxygen-containing derivatives from synthesis gas |
| GB0222240D0 (en) | 2002-09-25 | 2002-10-30 | Ici Plc | Cobalt catalysts |
| US7341976B2 (en) * | 2002-10-16 | 2008-03-11 | Conocophillips Company | Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using |
| WO2004035511A2 (en) * | 2002-10-16 | 2004-04-29 | Conocophillips Company | Fischer-tropsch processes and catalysts using stabilized supports |
| US7176160B2 (en) * | 2002-10-16 | 2007-02-13 | Conocophillips Company | Method for forming a Fischer-Tropsch catalyst using a boehmite support |
| CA2500546A1 (en) * | 2002-10-16 | 2004-04-29 | Conocophillips Company | Fischer-tropsch processes and catalysts made from a material comprising boehmite |
| CA2500553A1 (en) * | 2002-10-16 | 2004-04-29 | Conocophillips Company | A stabilized transition alumina catalyst support from boehmite and catalysts made therefrom |
| CA2500549A1 (en) * | 2002-10-16 | 2004-04-29 | Conocophillips Company | High hydrothermal stability catalyst support |
| WO2005005033A2 (en) * | 2003-06-30 | 2005-01-20 | New Jersey Institute Of Technology | Catalysts and methods for making same |
| US7541310B2 (en) * | 2003-10-16 | 2009-06-02 | Conocophillips Company | Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same |
| US7186757B2 (en) * | 2003-10-16 | 2007-03-06 | Conocophillips Company | Silica-alumina catalyst support with bimodal pore distribution, catalysts, methods of making and using same |
| GB2410449B (en) * | 2004-01-28 | 2008-05-21 | Statoil Asa | Fischer-Tropsch catalysts |
| GB0410408D0 (en) * | 2004-05-11 | 2004-06-16 | Johnson Matthey Plc | Catalysts |
| GB0426473D0 (en) | 2004-12-03 | 2005-01-05 | Johnson Matthey Plc | Catalysts |
| GB0501783D0 (en) * | 2005-01-28 | 2005-03-09 | Johnson Matthey Plc | Catalysts and preparation method |
| GB0503818D0 (en) * | 2005-02-25 | 2005-04-06 | Johnson Matthey Plc | Catalysts |
| GB0506976D0 (en) | 2005-04-06 | 2005-05-11 | Johnson Matthey Plc | Catalyst supports |
| GB2446127A (en) * | 2007-01-30 | 2008-08-06 | Gtl F1 Ag | Preparation of Fischer-Tropsch Catalysts |
| US8216963B2 (en) | 2008-12-29 | 2012-07-10 | Chevron U.S.A. Inc. | Preparation of cobalt-ruthenium fischer-tropsch catalysts |
| GB2473071B (en) | 2009-09-01 | 2013-09-11 | Gtl F1 Ag | Fischer-tropsch catalysts |
| GB2475492B (en) | 2009-11-18 | 2014-12-31 | Gtl F1 Ag | Fischer-Tropsch synthesis |
| FR2963345B1 (en) | 2010-07-29 | 2012-07-27 | IFP Energies Nouvelles | PROCESS FOR THE SYNTHESIS OF C5 + HYDROCARBONS IN THE PRESENCE OF A CATALYST PREPARED BY MEANS OF AT LEAST ONE CYCLIC OLIGOSACCHARIDE |
| FR2963344B1 (en) | 2010-07-29 | 2012-07-27 | IFP Energies Nouvelles | METHOD OF SELECTIVE HYDROGENATION IN THE PRESENCE OF A CATALYST BASED ON A GROUP VIII METAL PREPARED BY MEANS OF AT LEAST ONE CYCLIC OLIGOSACCHARIDE |
| WO2012020210A2 (en) | 2010-08-09 | 2012-02-16 | Gtl.F1 Ag | Fischer-tropsch catalysts |
| FR3011844A1 (en) | 2013-10-16 | 2015-04-17 | IFP Energies Nouvelles | SELECTIVE HYDROGENATION PROCESS USING CATALYST CONTAINING COPPER AND AT LEAST ONE METAL SELECTED FROM NICKEL OR COBALT |
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| US11426717B2 (en) * | 2014-11-17 | 2022-08-30 | The Regents Of The University Of Colorado, A Body Corporate | Catalyst, structures, reactors, and methods of forming same |
| CN106582662B (en) * | 2015-10-20 | 2019-03-22 | 中国石油化工股份有限公司 | Loaded catalyst and its preparation method and application and method by preparing low-carbon olefin |
| FR3050659B1 (en) | 2016-04-29 | 2021-09-03 | Ifp Energies Now | COBALT CATALYST BASED ON A SUPPORT CONTAINING A MIXED OXIDE PHASE CONTAINING COBALT AND / OR NICKEL PREPARED BY THE USE OF AN ESTER COMPOUND |
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| FR3056597A1 (en) | 2016-09-28 | 2018-03-30 | IFP Energies Nouvelles | HYDROTREATMENT PROCESS USING A CATALYST BASED ON A GROUP VIIIB METAL AND A GROUP VIB METAL PREPARED IN SUPERCRITICAL FLUID |
| FR3057472B1 (en) | 2016-10-17 | 2018-11-16 | IFP Energies Nouvelles | COBALT CATALYST BASED ON A SUPPORT CONTAINING A MIXED OXIDE PHASE CONTAINING COBALT AND / OR NICKEL PREPARED BY USING A HYDROGENOCARBON COMPOUND |
| US11493274B2 (en) | 2019-12-04 | 2022-11-08 | Greyrock Technology, Llc | Process for the commercial production of high-quality catalyst materials |
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| FR3087671B1 (en) | 2018-10-25 | 2023-09-29 | Ifp Energies Now | COBALT CATALYST BASED ON A SUPPORT COMPRISING A MIXED OXIDE PHASE CONTAINING COBALT AND/OR NICKEL PREPARED FROM AN ETHER COMPOUND |
| KR102352363B1 (en) | 2019-12-06 | 2022-01-17 | 한국세라믹기술원 | Manufacturing method of cobalt aluminum oxide |
| KR102241091B1 (en) | 2019-12-13 | 2021-04-19 | 한국세라믹기술원 | Manufacturing method of cobalt aluminum oxide |
| FR3119556A1 (en) | 2021-02-11 | 2022-08-12 | IFP Energies Nouvelles | Process for preparing a Fischer-Tropsch catalyst in the presence of an additive and a specific calcination step |
| CN113546627B (en) * | 2021-07-30 | 2022-12-09 | 宁夏大学 | Low-temperature carbon dioxide methanation catalyst and preparation method and application thereof |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB926235A (en) † | 1959-10-01 | 1963-05-15 | Chemetron Corp | Catalyst and the production thereof |
| US3883444A (en) * | 1971-07-20 | 1975-05-13 | Grace W R & Co | Auto exhaust catalyst |
| JPS51104488A (en) * | 1975-03-13 | 1976-09-16 | Toyota Motor Co Ltd | Shokubaitantai oyobi shokubai |
| SU728222A1 (en) * | 1977-07-01 | 1980-04-15 | Предприятие П/Я В-8584 | Voltage-to-code convertor |
| CA1140910A (en) * | 1979-01-02 | 1983-02-08 | James L. Carter | Supported cobalt-silica coprecipitated hydrogenation catalyst |
| CA1146930A (en) * | 1979-11-06 | 1983-05-24 | Allan E. Barnett | Production and use of novel non-ferrous group viii aluminum coprecipitated hydrogenation catalysts |
| GB2101005B (en) * | 1981-06-02 | 1984-09-05 | Asia Oil Co Ltd | Hydrogenation catalyst |
| US4605679A (en) † | 1981-10-13 | 1986-08-12 | Chevron Research Company | Activated cobalt catalyst and synthesis gas conversion using same |
| NL8201696A (en) † | 1982-04-23 | 1983-11-16 | Unilever Nv | METHOD FOR PREPARING METHANATION CATALYSTS |
| US4927857A (en) * | 1982-09-30 | 1990-05-22 | Engelhard Corporation | Method of methanol production |
| NL190602C (en) * | 1983-12-06 | 1994-05-16 | Unilever Nv | Process for preparing a nickel / nickel silicate catalyst and process for hydrogenating organic compounds therewith. |
| FR2556235A1 (en) * | 1983-12-09 | 1985-06-14 | Pro Catalyse | METHOD FOR MANUFACTURING AN ALUMINA BASED CATALYST |
| NL8501945A (en) * | 1984-12-07 | 1986-07-01 | Unilever Nv | CATALYST SUITABLE FOR DESULFULDIFYING AND PREPARING THIS CATALYST. |
| US4717702A (en) † | 1985-04-26 | 1988-01-05 | Shell Internationale Research Maatschappij Bv | Catalyst for conversion of synthesis gas to diesel fuel and process for preparation of such catalyst |
| DE3770920D1 (en) * | 1986-12-03 | 1991-07-25 | Catalyst And Chemicals Inc Far | FIRE-RESISTANT CATALYST AND METHOD FOR THE PRODUCTION THEREOF. |
| US5268091A (en) * | 1989-08-08 | 1993-12-07 | Institut Francais De Petrole | Method for removing arsenic and phosphorus contained in liquid hydrocarbon cuts, nickel based retaining material |
| SU1728222A1 (en) * | 1990-03-19 | 1992-04-23 | Мариупольский металлургический институт | Method of obtaining cobalt acetate |
| US5358633A (en) * | 1993-05-28 | 1994-10-25 | Texaco Inc. | Hydrodesulfurization of cracked naphtha with low levels of olefin saturation |
-
1994
- 1994-08-02 GB GB9415554A patent/GB9415554D0/en active Pending
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1995
- 1995-07-17 CN CN95194467A patent/CN1089632C/en not_active Expired - Lifetime
- 1995-07-17 DK DK95926949T patent/DK0775018T4/en active
- 1995-07-17 AU AU31151/95A patent/AU3115195A/en not_active Abandoned
- 1995-07-17 WO PCT/EP1995/002836 patent/WO1996004072A1/en active IP Right Grant
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- 1995-07-17 JP JP50613396A patent/JP3514463B2/en not_active Expired - Lifetime
- 1995-07-17 US US08/776,570 patent/US5874381A/en not_active Expired - Lifetime
- 1995-07-17 DE DE69527069T patent/DE69527069T3/en not_active Expired - Lifetime
- 1995-07-17 AT AT95926949T patent/ATE218920T1/en not_active IP Right Cessation
- 1995-07-17 KR KR1019970700694A patent/KR100366385B1/en not_active IP Right Cessation
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007038217A (en) * | 2005-07-30 | 2007-02-15 | Oxeno Olefinchemie Gmbh | Hydrogenation catalyst, and catalytic hydrogenation method for ester-containing aldehyde mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| DK0775018T4 (en) | 2009-01-26 |
| DE69527069T2 (en) | 2002-10-02 |
| AU3115195A (en) | 1996-03-04 |
| DE69527069D1 (en) | 2002-07-18 |
| MX9700735A (en) | 1997-09-30 |
| CN1154667A (en) | 1997-07-16 |
| EP0775018B1 (en) | 2002-06-12 |
| US5874381A (en) | 1999-02-23 |
| EP0775018B2 (en) | 2008-11-26 |
| ATE218920T1 (en) | 2002-06-15 |
| CN1089632C (en) | 2002-08-28 |
| GB9415554D0 (en) | 1994-09-21 |
| JP3514463B2 (en) | 2004-03-31 |
| DE69527069T3 (en) | 2009-06-25 |
| WO1996004072A1 (en) | 1996-02-15 |
| DK0775018T3 (en) | 2002-09-30 |
| KR100366385B1 (en) | 2003-05-16 |
| BR9508465A (en) | 1997-12-30 |
| EP0775018A1 (en) | 1997-05-28 |
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